Perovskite quantum dot material

ABSTRACT

Provided is a hybridized perovskite quantum dot material. The quantum dot material includes a kernel and surface ligands. The kernel is formed by R 1 NH 3 AB 3  or (R 2 NH 3 ) 2 AB 4 , where R 1  is methyl group, R 2  is an organic molecular group, A is at least one selected from Ge, Sn, Pb, Sb, Bi, Cu and Mn, B is at least one selected from Cl, Br and I, A and B form a coordination octahedral structure, and R 1 NH 3  or R 2 NH 3  is filled in gaps of the coordination octahedral structure. The surface ligand is an organic acid or organic amine. The quantum dot material has a high fluorescence quantum yield.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation Application of U.S. patentapplication Ser. No. 15/584,042 filed on May 2, 2017, which is aContinuation Application of PCT application No. PCT/CN2015/092497 filedon Oct. 22, 2015, which in turn claims the benefit of Chinese PatentApplication No. 201410612348.6 filed on Nov. 4, 2014. AU the above arehereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to material field, and in particular to aperovskite quantum dot material and preparation method thereof.

BACKGROUND

The general chemical formula of ideal inorganic perovskite is ABX₃, inwhich, the central metal cationic B and anion X form an octahedralstructure. A filled in gaps of the octahedral structure is configuredfor equilibrating charge of the anion BX₃. For a typicalthree-dimensional perovskite structure, when extracting severaloctahedral layers from the three-dimensional structure along a certaindirection, or replacing several octahedral layers with other components,then layered perovskite structure could appear. Organic-inorganichybridized perovskite material is formed by replacing atoms at A site onthe inorganic perovskite with organic amine, the organic amine is filledin gaps of each octahedral structure. Octahedral structures may beconnected with each other to form a network structure via a commonvertex. The organic amine may enter into the inorganic spatial by meansof hydrogen bonds formed by hydrogens at the organic amine and halideions. The organic chains are interacted with each other by Van Der Waalsforce to form a hybrid structure having alternating organic andinorganic layers. For the hybridized perovskite structure, the organicamine filled in the gaps of the inorganic octahedral structure needs tosatisfy the restriction of the tolerance factor t:(R_(A)+R_(X))=t√2(R_(B)+R_(X)), R_(A) is radius of A atoms, R_(B) andR_(X) are radii of corresponding element atoms. When the tolerancefactor t is in the range of 0.8≤t≤0.9, the three-dimensional perovskitestructure is formed. Therefore, the radii of A, B and X atoms determinewhether the organic amine chains can be filled in the gaps. For thehybridized perovskite structure in which the lead halide and tin halideform inorganic layers, being capable of forming the three-dimensionalstructure of short-chain amine, such as CH₃NH₃MX₃(M=Pb, Sn) andNH₂CH═NH₂SnI₃

Organic-inorganic hybridized perovskite material combines the advantagesof organic materials and inorganic materials on the molecular scale, notonly having good thermal stability, mechanical property andelectromagnetic property of the inorganic materials, but also beingeasily processed into a film. A quantum well structure is formed byalternately stacking the unique inorganic and organic layers of theorganic-inorganic hybridized perovskite material enable the hybridizedperovskite material to have a relatively high excitation binding energyunder dual effects of the quantum confinement and electric confinement,with the features of showing a distinct optical characteristics such ashigh charge carrier mobility and strong room-temperaturephotoluminescence, and having a relatively narrow half-peak width andhigh luminous purity. Furthermore, by controlling amount of organicmaterials and inorganic materials, the luminescence property of thehybridized perovskite material can be controlled. Therefore, thehybridized perovskite material has unique application value in thefields of field effect transistors, solar batteries,electro-luminescence, display devices and so on. Because of the uniqueproperty and application value of the hybridized perovskite material,the research on this kind of material has been drawn wide attention ofresearchers in recent years.

When size of the organic-inorganic hybridized perovskite material isdecreased to the nanometer scale, because quantum dot has a small sizeand owns surface ligands, the quantum dot may easily diffuse into commonsolutions, enabling the hybridized perovskite material to be processedand applied easily. Therefore, the hybridized perovskite material may beapplied in electro-optic fields through various ways. Meanwhile, due toits quantum confinement effect of the quantum dot, the organic-inorganichybridized perovskite quantum dot shows more excellent property thanbulk materials, such as a stronger luminescence intensity and higherquantum yield, and its luminescence wavelength can be adjusted bycontrolling the size of namo-particles. Compared to inorganic quantumdot material, the half-peak width of the organic-inorganic hybridizedperovskite quantum dot is narrower and its luminescence purity ishigher, which has big advantages in high performance display devices.The hybridized perovskite material could be a potential material formaking laser. Additionally, its layered self-assembly structure enablesthe hybridized perovskite material to own distinct nonlinear opticalproperty, which can be applied into nonlinear optical devices.Therefore, the organic-inorganic hybridized perovskite quantum dotmaterial owns a vital position in the field of the hybridized perovskitematerial.

Currently, the preparation method of the organic-inorganic hybridizedperovskite quantum dot is less to be reported. The hybridized perovskitequantum dot was manufactured by template method before. In 2012, AkihiroKojima et al. reported using porous alumina template to synthesizenanostructure CH₃NH₃PbBr₃ in Chemistry Letters. The method is injectinga precursor solution into nano-scale pores of the porous aluminatemplate, the growth of CH₃NH₃PbBr₃ particles are restricted by use ofthe nano-scale pores to obtain CH₃NH₃PbBr₃ quantum dot with luminescencewavelength at 523 nm. Even though using the method can make CH₃NH₃PbBr₃quantum dot, the CH₃NH₃PbBr₃ quantum dot is embedded in the aluminumoxide template and not suitable for future processing and application todevices. In 2014, Luciana C. Schmidt first reported using non-templatemethod to make nanostructure CH₃NH₃PbBr₃ on the Journal of AmericanChemistry Society. The method is using ODE (1-octadecene) as thesolution, wider the reaction temperature 80° C. adding methyl ammoniumbromide salts, long—chain amine bromide salts, lead bromide etc,dispersing the above-mentioned materials into the solution uniformly,finally adding acetone thereto, then the CH₃NH₃PbBr₃ particles areobtained via precipitation method. If the CH₃NH₃PbBr₃ particles withluminescence wavelength at 526 nm, the fluorescence quantum yieldreaches to 20%. However, the hybridized perovskite quantum dot materialstill has a low fluorescence quantum yield. The dispersibility ofquantum dot in solutions still needs to be improved. Nowadays, reportson the hybridized perovskite quantum dot material still focus onCH₃NH₃PbBr₃ quantum dot with luminescence wavelengths in the range of520-530 nm, the adjustment of the luminescence wavelength is verynarrow.

Therefore, even though the perovskite quantum dot material exhibits thephotoluminescence property and excellent optoelectronic property at theroom temperature, the perovskite quantum dot material still has a lowquantum yield. It is difficult for the perovskite quantum dot materialto disperse into solutions, meanwhile to prevent the structure fromdamage, which becomes one bottleneck that limits the development of theperovskite quantum dot material. Accordingly, improving the fluorescencequantum yield of the perovskite quantum dot material and obtaining gooddispersibility of perovskite solutions seem especially important.

SUMMARY

The present invention aims to solve at least one of the technicalproblems in the prior art.

In one aspect of the present invention, it discloses a hybridizedperovskite quantum dot material. According to an embodiment of thepresent invention, the quantum dot material includes: a kernel, formedby R₁NH₃AB₃ or (R₂NH₃)₂AB₄, in which, R₁ is a methyl group, R₂ is anorganic molecular group, A is one or more selected from a groupconsisting of Ge, Sn, Pb, Sb, Bi, Cu and Mn, B is one or more selectedfrom a group consisting of Cl, Br and I. A and B form a coordinationoctahedral structure, and R₁NH₃ or R₂NH₃ is filled in gaps of thecoordination octahedral structure; a surface ligand being an organicacid or organic amine. Therefore, the perovskite quantum dot material ofthe present invention may have a reasonable structure, to own moreexcellent properties.

According to an embodiment of the present invention, in the quantum dotmaterial, the ligands are divergent, wrapping out of the surface of thekernel, thus can restrict the growth of the kernel in three-dimensionsto keep the size of the quantum dot material in nano-scale.

According to an embodiment of the present invention, in the quantum dotmaterial, R₂ is a long-chain organic molecular group. Therefore, thepresent invention can disclose organic hybridized groups to the quantumdot material, so as to improve the structure of a quantum well of thequantum dot, and to improve the properties of the quantum dot material.

According to an embodiment of the present invention, in the quantum dotmaterial, the surface ligand is an organic acid or a long-chain organicamine which can adsorb the surface of the kernel via. Van Der WaalsForce, thus to achieve the purpose of restricting the size of thequantum dot material.

According to an embodiment of the present invention, in the quantum dotmaterial, the organic acid includes a saturated or an unsaturated alkylacid with at least three carbon atoms. So the growth of the kernel inthree dimensions can be restricted to keep the size of the quantum dotmaterial in nano-scale, by use of the organic acid wrapping out of thesurface of the kernel of the quantum dot material.

According to an embodiment of the present invention, in the quantum dotmaterial, the molecular formula of the long-chain organic amine is RNH₂in which R is a saturated linear or branched alkyl group, or anunsaturated linear or a branched alkyl group. Therefore, it is possibleto restrict the growth of the kernel in three dimensions so as to keepthe size of the quantum dot material in nano-scale, by use of thelong-chain organic amine wrapping out of the surface of the kernel ofthe quantum dot material.

According to an embodiment of the present invention, in the quantum dotmaterial, the long-chain organic amine is an alkyl or aryl amine withfrom 4 to 24 carbon atoms, to restrict the growth of the kernel in threedimensions while to ensure that the stability of the quantum dotmaterial will not be affected, thereby to improve the properties of thequantum dot material.

One aim of the present invention is to disclose a hybridized perovskitequantum dot material that has a high fluorescence quantum yield. It issuitable for a variety of hybridized perovskite quantum dots andluminescence wavelengths can cover the entire visible region. Thehybridized perovskite quantum dot material that has a high fluorescencequantum yield includes: a kernel which is formed by R₁NH₃AB₃ or(R₂NH₃)₂AB₄, where A and B form a coordination octahedral structure,R₁NH₃ or R₂NH₃ is filled in gaps of the coordination octahedralstructure, R₁ is methyl, R₂ is a long-chain organic molecular group, Ais one or more selected from a group consisting of Ge. Sn, Ph, Sb, Bi,Cu and Mn, and B is one or more selected from a group consisting of Cl,Br and I; and surface ligands that are divergent, wrapping out of thesurface of the kernel, and the surface ligand is an organic acid or along-chain organic amine. In this hybridized perovskite quantum dotmaterial, the organic acid is a saturated alkyl acid that its formula isC_(n)H_(2m+1)COOH (n≥2), or an unsaturated alkyl acid that its formulais C_(n)H_(2n−1)COOH (n≥2). In above-mentioned hybridized perovskitequantum dot material, a molecular formula of the long-chain organicamine is RNH₂, in which R is a saturated linear or a branched alkylgroup, or an unsaturated linear or a branched alkyl group.

In another aspect of the present invention, it discloses a method formaking a hybridized perovskite quantum dot material. According to anembodiment of the present invention, the method includes followingsteps: (1) dissolving an inorganic metal halide and an organic ammoniumhalide in a first solvent to obtain a precursor solution, in which boththe inorganic metal halide and the organic ammonium halide exist in theform of free molecules; and (2) dropping the precursor solution into asecond solvent dropwise, in which, the solubility of the inorganic metalhalide and the organic ammonium halide in the first solvent is differentfrom that in the second solvent to allow the inorganic metal halide andthe organic ammonium halide to be self-assembled, so that an inorganicmetal cation of the inorganic metal halide and halogen anions of theorganic ammonium halide form a coordination octahedral structure, andorganic ammonium cations of the organic ammonium halide enter into gapsof the coordination octahedral structure to obtain the hybridizedperovskite quantum dot material, of which, a surface ligand has beenadded in advance to one or more selected from a group consisting of thefirst solvent and the second solvent, and the surface ligand is anorganic acid or a long-chain organic amine. In that case, it is possibleto simply make the hybridized perovskite quantum dot material, whileallow it to have a relatively high fluorescence quantum yield.

According to an embodiment of the present invention, the first solventincludes one or more selected from a group consisting of N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, N-methylpyrrolidinone and acetone. The second solvent includes one or moreselected from a group consisting of toluene, chloroform, n-hexane,cyclohexane, ethyl acetate, and diethyl ether. Therefore, it is possibleto make the solubility of the inorganic metal halide and the organicammonium halide in the first solvent different from that in the secondsolvent, thus promoting self-assembly of the inorganic metal halide andthe organic ammonium halide, thus simply making the hybridizedperovskite quantum dot material and allowing the quantum dot material tohave a relatively high fluorescence quantum yield.

According to an embodiment of the present invention, the first solventand the second solvent are miscible. Thus, it is possible to fulfill theself-assembly of the inorganic metal halide and the organic ammoniumhalide so as to improve the efficiency and effect of making the quantumdot material by this method, by easily adding the precursor solutioncontaining the first solvent to the second solvent.

According to an embodiment of the present invention, the organic acidincludes a saturated or an unsaturated alkyl acid with at least threecarbon atoms; and a molecular formula of the long chain organic amine isRNH₂ in which R is a saturated linear or branched alkyl group, or anunsaturated linear or a branched alkyl group. Therefore, it is possibleto select an organic amine with an appropriate structure as thelong-chain organic amine surface ligand according to different inorganicmetal halides, so as to simply make the hybridized perovskite quantumdot material while allow the quantum dot material to have a relativelyhigh fluorescence quantum yield.

According to an embodiment of the present invention, the long chain inthe long-chain organic amine is an alkyl or aryl group with from 4 to 24carbon atoms. Therefore, it is possible to select an organic amine withan appropriate structure as the long-chain organic amine surface ligandaccording to different inorganic metal halides, so as to simply make thehybridized perovskite quantum dot material while allow the quantum dotmaterial to have a relatively high fluorescence quantum yield.

According to an embodiment of the present invention, the precursorsolution may be obtained by following steps: (a) mixing the inorganicmetal halide and the organic ammonium halide in which a molar ratio is1:(0.1˜3), and adding the long-Chain organic amine, the molar ratio ofthe long-chain organic amine to the inorganic metal halide is (0.1˜3):1;in which, the inorganic metal halide is one or more selected from agroup consisting of halides of Ge, Sn, Pb, Sb, Bi, Cu and Mn, and thehalide includes one or more selected from a group consisting ofchloride, bromide and iodide; (b) adding the organic acid to the mixedsolution obtained in step (a), the molar ratio of the organic acid tothe inorganic metal halide is (0˜20):1, and adding the first solvent;the a molar ratio of the first solvent to the inorganic metal halide is(20˜1000):1; and (c) performing ultrasonic treatment to mixed solutionobtained in step (b), then filtering the ultrasound-treated mixedsolution with a 0.2 μm-pore size polytetrafluoroethylene (referred to asPTFE) filter head, and retaining the filtrate to obtain the precursorsolution. In this case, it is possible to simply make the precursorsolution so as to improve the preparation efficiency of the method.

According to an embodiment of the present invention, the organicammonium halide is obtained by the following steps: dissolving anorganic amine in absolute ethanol to prepare a solution in which thevolume of the organic amine accounts for 40%, and stirring well, in anice water bath environment, adding a haloid acid to the solution whilestirring, the molar ratio of the organic amine to the haloid acid is1:(1˜3), and continuously stirring for 2 hours in the ice water bathenvironment, then evaporating the solution with a rotary evaporator at50 centigrade under a pressure of −0.1 MPa to remove the solvent andobtain powders of the organic ammonium halide, then washing the powdersof the organic ammonium halide three times with diethyl ether, filteringthen obtaining a residue, and drying the residue in a vacuum drying ovenat 50 centigrade under a pressure of −0.1 MPa for 4 hours to obtain theorganic ammonium halide, in which, the haloid acid includes one or moreselected from a group consisting of HCl, HBr and HI, and the organicamine is a saturated alkyl amine that its formula is C_(n)H_(2n+1)NH₂(n≥1) and an unsaturated alkyl or an aryl amine that its formula isC_(n)H_(2n−1)NH₂ (n≥2).

According to an embodiment, step (2) further includes: (2-1) droppingthe precursor solution into the second solvent, dropwise, at an addingspeed 10 μL to 1 mL per minute while stirring, a volume ratio of theadded precursor solution to the second solvent is 1:(0.0001˜10), andcontinuously stirring for 2 hours to obtain a suspension solution; (2-2)centrifuging the suspension solution with a centrifuge at a rotationalspeed of 7500 rpm for 4 minutes to obtain supernatant containing thehybridized perovskite quantum dot material; and (2-3) distilling thesupernatant to dryness and then drying the remaining solid at 70centigrade under a pressure −0.1 MPa for 8 hours to obtain thehybridized perovskite quantum dot material. Therefore, it is possible toallow the inorganic metal halide and the organic ammonium halide to beself-assembled thus simply obtain the hybridized perovskite quantum dotmaterial by adding the second solvent.

The principle of the method of the present invention for making thehybridized perovskite quantum dot material is: both the inorganic metalhalide and the organic ammonium halide are soluble in the first solvent,and they exist therein in the form of free molecules. When the precursorsolution is dropped into the second solvent, they will soon beself-assembled: an inorganic metal cation and halogen anions will form acoordination octahedral structure, and organic ammonium cations willenter into gaps of the coordination octahedral structure to form ahybridized perovskite structure; meanwhile, due to the existence ofoleic acid, long-chain organic amine and some other ligands in thesolution, these ligands will wrap out of surfaces of the formedparticles and restrict the growth of the particles in three dimensions,thereby limiting the size of the particles in nano-scale, and finallyresulting in the formation of the hybridized perovskite quantum dots. Inthe preparation method of the present invention, it is possible to makehybridized perovskite quantum dots with different luminescencewavelengths by adjusting the ratio of the inorganic halide to thelong-chain organic amines; it is possible to make the hybridizedperovskite quantum dots having different components by adjusting varietyand ratio of the first solvent to the second solvent. In the preparationmethod of the present invention, the surface ligands may be added to thefirst solvent or to the second solvent; the organic-inorganic hybridizedperovskite fluorescence quantum dot made via the method of the presentinvention, is wrapped with organic ligands out of its surface, may bestably dispersed in the second solvent, which facilitates the processingand application of the hybridized perovskite quantum dot, and thehybridized perovskite quantum dot material can be obtained by removal oforganic solvents through distillation.

In another aspect of the present invention, it provides a method formaking the hybridized perovskite quantum dot material as describedearlier. According to an embodiment of the present invention, the methodincludes: (1) dissolving an organic amine in absolute ethanol to preparea solution that the volume of the organic amine accounts for 40%, andstirring for 10 minutes until homogeneous; in an ice water bathenvironment, adding the haloid acid to the solution, a molar ratio ofthe organic amine to the haloid acid is 1:(1˜3) while stirring, andcontinuously stirring for 2 hours in the ice water bath environment toobtain a clear solution; evaporating the solution with a rotaryevaporator at 50 centigrade under a pressure −0.1 MPa to remove thesolvent and obtain crystalline powder of the organic ammonium halide;washing the crystalline powder three times with diethyl ether,filtering, and drying in a vacuum drying oven at 50 centigrade under apressure −0.1 MPa for 4 hours to obtain powder of the organic ammoniumhalide, wherein the organic amine is a saturated alkyl amine that itsformula is C_(n)H_(2n+1)NH₂ (n≥1) or an unsaturated alkyl or aryl aminethat its formula is C_(n)H_(2n−1)NH₂ (n≥2); (2) mixing the inorganicmetal halide and the organic ammonium halide powder that a molar ratioof the inorganic metal halide to the organic ammonium halide power is1:(0.1˜3), adding a long-chain organic amine as described above where amolar ratio of the long-chain organic amine to the inorganic metalhalide is 1:(0.1˜3), then adding an organic acid as described abovewhere a molar ratio of the organic acid to the inorganic metal halide is1:(0˜20), and then adding a first solvent that a molar ratio of thefirst solvent to the inorganic metal halide is 1:(20˜1000); aftermixing, performing ultrasonic treatment to the mixture for 5 minutes toobtain a transparent mixed solution, and filtering the transparent mixedsolution with 0.2 μm-pore size PTFE filter head to obtain filtrate as aprecursor solution; in this step, the inorganic metal halide is one andonly one selected from a group consisting of halides of Ge, Sn, Pb, Sb,Bi, Cu and Mn, and the first solvent is one and only one selected from agroup consisting of N,N-dimethyl formamide, dimethyl sulfoxide,tetrahydrofuran, acetonitrile, and acetone; (3) placing a second solventon a magnetic mixer to be fast stirred, dropping the precursor solutioninto the second solvent via a microsyringe at an adding speed 10 μL to 1mL per minute, dropwise while stirring, where the volume ratio of theprecursor solution to the second solvent is 1:(0.0001˜10), andcontinuously stirring for 2 hours to obtain a suspension oforganic-inorganic hybridized perovskite material, of which the secondsolvent is one and only one selected from a group consisting of toluene,chloroform, n-hexane, cyclohexane, ethyl acetate, and diethyl ether,selectively, the first solvent and the second solvent are miscible; (4)centrifuging the suspension of organic-inorganic hybridized perovskitematerial obtained in step (3) with a centrifuge at a rotational speed7500 rpm for 4 minutes to obtain precipitate which is hybridizedperovskite nanosheets or nanorods and supernatant which is a hybridizedperovskite quantum dot solution; (5) distilling the hybridizedperovskite quantum dot solution obtained in step (4) to remove theorganic solvents, and drying the remaining solid in a vacuum di ringoven at 70 centigrade under a pressure −0.1 MPa for 8 hours to obtainthe hybridized perovskite quantum dot material. Therefore, it ispossible to simply make the hybridized perovskite quantum dot materialand thus to improve the efficiency of making the quantum dot material.

In another aspect of the present invention, it discloses a hybridizedperovskite quantum dot material which is made according to the method ofthe present invention described above. Therefore, the quantum dot hasall properties and advantages of the quantum dot made using theabove-described method, which will not be described in detail here.

In another aspect of the present invention, it discloses a method formaking the above-mentioned hybridized perovskite quantum dot material.According to an embodiment of the present invention, the methodincludes: (1) dissolving an inorganic metal halide and an organicammonium halide or a halide of cesium in a first solvent to obtain aprecursor solution, in which the inorganic metal halide, the organicammonium halide or the halide of cesium exist in a dispersed form; (2)adding the precursor solution to a second solvent to form an emulsionsystem, where a surface ligand has been added in advance to one or moreselected from a group consisting of the first solvent and the secondsolvent and the surface ligand is an organic acid or a long-chainorganic amine; and the first solvent and the second are immiscible, theemulsion system contains micelles formed by the surface ligand, theprecursor solution is encapsulated in the micelles, and the micelles aredispersed in the second solvent; and (3) adding a demulsifier to theemulsion system so that the precursor solution in the micelles isdiffused into the second solvent, enabling the inorganic metal halide,and the organic ammonium halide or halide of cesium to beself-assembled; an inorganic metal cation of the inorganic metal halide,and the halogen anions of the organic ammonium halide or halide ofcesium form a coordination octahedral structure; and organic ammoniumcations of the organic ammonium halide enter into gaps of thecoordination octahedral structure to form the perovskite quantum dotmaterial, of which the inorganic metal halide is one or more selectedfrom a group consisting of halides of Ge, Sn, Pb, Sb, Bi, Cu and Mn, thehalide includes one or more selected from a group consisting ofchloride, bromide and iodide, the first solvent is one or more selectedfrom a group consisting of N,N-dimethyl formamide, acetonitrile,N-methyl pyrrolidinone and dimethyl sulfoxide, the second solvent is oneor more selected from a group consisting of 1-octadecene, n-hexane,cyclohexane and n-heptane, and a surface ligand has been added inadvance to one or more selected from a group consisting of the firstsolvent and the second solvent, and the surface ligand is an organicacid or a long-chain organic amine.

According to an embodiment of the present invention, in this method, theorganic acid includes a saturated or unsaturated alkyl acid with atleast three carbon atoms, and the molecular formula of the long-chainorganic amine is RNH₂ in which R is a saturated linear or a branchedalkyl group, or an unsaturated linear or a branched alkyl group.Therefore, it is possible to use the above-mentioned organic acids asthe surface ligands and thus to improve the properties of the quantumdot material prepared.

According to an embodiment of the present invention, in this method, thelong-chain organic amine is an alkyl or aryl amine with from 4 to 24carbon atoms. Therefore, it is possible to use the above-mentionedorganic acids as the surface ligands and thus to improve the propertiesof the quantum dot material prepared.

According to an embodiment of the present invention, the precursorsolution is obtained by the following steps: mixing the inorganic metalhalide that the molar ratio of the organic ammonium halide to the halideof cesium is 1:(0.1˜3), adding the long-chain organic amine that theratio of the long-chain organic amine to the inorganic metal halide is(0.1˜3):1, adding the organic acid that the molar ratio of the organicacid to the inorganic metal halide is (0˜20):1, adding the first solventthat the molar ratio of the first solvent to the inorganic metal halideis (20˜1000) to 1 to form a mixed solution, and performing ultrasonictreatment to the mixed solution, then filtering with a 0.2 μm-pore sizePTFE filter head, retaining filtrate to obtain the precursor solution.In this case, it is possible to obtain a precursor solution and thussimply obtain a perovskite quantum dot material in subsequent steps.

According to an embodiment of the present invention, the organicammonium halide is obtained by the following steps: dissolving anorganic amine in absolute ethanol to prepare a solution which the volumeof the organic amine accounts for 40%, and stirring well; in the icewater bath environment, adding a haloid acid to the solution where themolar ratio of the organic amine to the haloid acid is 1:(1˜3) whilestirring, and continuously stirring for 2 hours in the ice water bathenvironment; evaporating the solution with a rotary evaporator at 50centigrade under a pressure −0.1 MPa to remove the solvent and obtainpowder of the organic ammonium halide; washing the organic ammoniumhalide powder three times with diethyl ether, filtering to obtain aresidue and drying the residue in a vacuum drying oven at 50 centigradeunder a pressure −0.1 MPa for 4 hours to obtain the organic ammoniumhalide, in which the haloid acid includes one or more selected from agroup consisting of HCl, HBr and HI, and the organic amine is one ormore selected from a group consisting of methylamine, formamide, andacetamine. Therefore, it is possible to simply obtain the organicammonium halide and thus to improve the efficiency and effect of makingthe perovskite quantum dot material using this method.

According to an embodiment of the present invention, step (2) furtherincludes: dropping the precursor solution into the second solvent,dropwise at an adding speed 10 μL to 1 mL per minute while stirring,where the volume ratio of the added precursor solution to the secondsolvent is 1:(0.0001˜10), and continuously stirring for 2 hours toobtain the emulsion system. Therefore, it is possible to obtain anemulsion system and thus to improve the efficiency and effect ofpreparing the perovskite quantum dot material using this method.

According to an embodiment of the present invention, step (3) furtherincludes: adding a demulsifier to the emulsion system where the volumeratio of the demulsifier to the second solvent is 1:(1˜10), centrifugingthe obtained emulsion system with a centrifuge at a rotational speed7500 rpm for 4 minutes to obtain supernatant so as to obtain ahybridized perovskite quantum dot solution, washing the hybridizedperovskite quantum dot solution and drying under vacuum to obtain theperovskite quantum dot material, of which, the demulsifier is one ormore selected from a group consisting of acetone, methanol, isopropanol,n-butanol and tert-butanol. Therefore, it is possible to obtain thehybridized perovskite quantum dot material simply by the self-assemblyprocess and adding the demulsifier, and thus to improve the efficiencyand effect of preparing the perovskite quantum dot material using thismethod.

In another aspect of the present invention, it discloses a semiconductordevice. According to an embodiment of the present invention, the deviceincludes the aforementioned hybridized perovskite quantum dot material.Therefore, the quantum dot material can provide quantum dots with areasonable structure and good properties to the semiconductor device,and thus to improve effect of use of the semiconductor device.

According to an embodiment of the present invention, the semiconductordevice includes electroluminescent devices, solar batteries, displaydevices and non-linear optical devices. Therefore, the quantum dotmaterial according to embodiments of the present invention can beapplied to corresponding positions of the devices, performingcorresponding functions thus improving effect of use of the devices.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a structural schematic diagram of a hybridized perovskitequantum dot material according to one embodiment of the presentinvention;

FIG. 2 is an emission spectrum of quantum dot according to theembodiment 1 of the present invention;

FIG. 3 is digital images of a quantum dot solution under a fluorescentlamp and an ultraviolet lamp according to the embodiment 3 of thepresent invention;

FIG. 4 is an absorption spectrum and an emission spectrum of the quantumdot according to the embodiment 3 of the present invention;

FIG. 5 is a scanning electron microscopy image of a precipitateaccording to the embodiment 3 of the present invention;

FIG. 6 is a transmission electron microscopy image of the quantum dotsaccording to the embodiment 3 of the present invention;

FIG. 7 is digital images of a quantum dot solution under a fluorescentlamp and an ultraviolet lamp according to the embodiment 5;

FIG. 8 is an emission spectrum of the quantum dot according to theembodiment 5 of the present invention;

FIG. 9 is an emission spectrum of quantum dot according to theembodiment 8 of the present invention;

FIG. 10 is a structural schematic diagram of an electroluminescentdevice according to the embodiment 8 of the present invention;

FIG. 11 is a flow chart of a method for making a hybridized perovskitequantum dot material according to one embodiment of the presentinvention;

FIG. 12 is a flow chart of a method for making a hybridized perovskitequantum dot material according to another embodiment of the presentinvention; and

FIG. 13 is a flow chart of a method for making a hybridized perovskitequantum dot material according to another embodiment of the presentinvention.

DESCRIPTION OF REFERENCE SIGNS

-   -   1. surface ligand    -   2. kernel    -   3. octahedron    -   4. organic amine    -   5. Al electrode    -   6. Hole transport layer    -   7. quantum dot light-emitting layer    -   8. Titanium diisopropoxide bis(acetylacetonate) layer    -   9. Indium tin oxide laser    -   10. glass substrate

DETAILED DESCRIPTION OF THE EMBODIMENTS

Embodiments of the present invention will be described in detail below,of which examples are illustrated in the drawings, throughout whichidentical or similar signs indicate identical or similar elements orelements having identical or similar functions. It should be understoodthat the specific embodiments described herein are merely used fordescribing the present invention, but are not intended to limit thepresent invention.

In one aspect of the present invention, it provides a hybridizedperovskite quantum dot material. According to an embodiment of thepresent invention, referring to FIG. 2, the quantum dot materialincludes surface ligands 1 and a kernel 2. Specifically, according to anembodiment of the present invention, the kernel 2 is formed by R₁NH₃AB₃or (R₂NH₃)₂AB₄, in which A is a central metal cation and B is a halogenanion. The central metal cations A and the halogen anions B form aregular octahedron 3, and an organic amine 4, i.e., R₁NH₃ or R₂NH₃, isfilled in gaps of the octahedron 3. Furthermore, the surface ligands 1are adsorbed on a surface of the kernel 2 via Van Der Waal forces. Inthis way, each octahedron 3 in the kernel 2 is connected and extendedvia common vertexes, and the organic amine 4 enters into gaps of theregular octahedron 3 by means of hydrogen bonds formed by hydrogens atthe organic amine and the halogen anion B, of which organic andinorganic layers are alternately arranged as a hybridized structure,thus has combined advantages of the inorganic and organic material on amolecular scale. Furthermore, the quantum dot material has a relativelyhigh fluorescence quantum yield, thereby improving the photoelectricperformance and enlarging range of use of the quantum dot materialaccording to embodiments of the present invention.

According to an embodiment of the present invention, A is one or moreselected from a group consisting of Ge, Sn, Pb, Sb, Bi, Cu and Mn, B isone or more selected from a group consisting of Cl, Br and I, R₁ ismethyl, and R₂ is a long-chain organic molecular group. Specifically,according to an embodiment of the present invention, Ft, is an alkyl oran aryl group with at least two carbon atoms. Therefore, based on actualmetal element and halogen for forming the quantum dot material and thesize of the gap of the regular octahedron 3 for forming the kernel 2,being able to choose an appropriate organic amine 4 with R₁ or R₂ groupsfor filling, thus to increase the stability of the quantum dot materialaccording to the embodiment of the present invention. Furthermore,adjustment of luminescence wavelength of the quantum dot may be realizedby selecting components constituting the quantum dot.

According to an embodiment of the present invention, surface ligands 1is carried on the surface of the kernel 2. According to an embodiment ofthe present invention, the surface ligands 1 are an organic acid or along-chain organic amine, and they are divergent, wrapping out of thesurface of the kernel 2. Thus, the surface ligands 1 may restrict thegrowth of the kernel 2 in three dimensions so as to keep the size of thequantum dot material in the nano-scale.

Specifically, the organic acid for forming the surface ligand 1 may be asaturated or unsaturated alkyl acid with at least three carbon atoms.According to some embodiments of the present invention, the organic acidmay be a saturated alkyl acid that the formula is C_(n)H_(2n+1)COOH(n≥2), or an unsaturated alkyl acid that the formula isC_(n)H_(2n−1)COOH (n≥2); the long-chain organic amine that the molecularformula may be RNH₂, for forming the surface ligand 1, of which R is asaturated linear or a branched alkyl group, or an unsaturated linear ora branched alkyl group. More specifically, R may be an alkyl or arylgroup containing from 4 to 24 carbon atoms. By the aforementionedorganic acid or long-chain organic amine forming the surface ligand 1,the size of the quantum dot material can be limited while the stabilityof the quantum dot material can be ensure, therefore, improving theperformance of the quantum dot material.

Furthermore, according to an embodiment of the present invention, thequantum dot material has particles with size of 3 to 4 nm. Furthermore,by means of an integrating sphere instrument for measurement of quantumyield (C9920-02, Hamamatsu Photonics) and according to a methoddescribed in the instruction from its manufacturer, inventors testedfluorescence quantum yields of quantum dot materials made according toembodiments 1-13 of the present invention. The quantum dot materialsaccording to the embodiments of the present invention could havefluorescence quantum yields not lower than 60%, which is higher thanthat of the conventional hybridized perovskite quantum dot material.Moreover, according to an embodiment of the present invention, thequantum dot material can also be stably dispersed in a variety oforganic solvents such as toluene, chloroform, n-hexane, cyclohexane andethyl acetate, and both the powder and solution of the quantum dots havegood stability, and the fluorescence remains a long time withoutquenching. Meanwhile, being able to select different metal elements,halogens and surface ligands, the component and structure of the quantumdot material can be determined accordingly to make quantum dots withdifferent luminescence wavelengths that can cover the entire visibleregion, which allows the quantum dots to have great advantages whenapplied to high color gamut white light LEDs. For example, by adjustingratios of inorganic metal halide to the long-chain organic amine,hybridized perovskite quantum dots having different luminescencewavelengths can be made; and by adjusting variety and ratio of the firstsolvent to the second solvent, hybridized perovskite quantum dots havingdifferent components can be made. Further, the quantum dot materialaccording to an embodiment of the present invention has a relativelynarrow half-peak width while emits high color-purity light, can meetrequirements in actual application, and owns a wide application prospectin fields of high-performance display devices, laser, non-linear optics,etc.

In another aspect of the present invention, it provides a method formaking a hybridized perovskite quantum dot material. According to anembodiment of the present invention, referring to FIG. 11, the methodincludes:

S100: obtaining a precursor solution

According to an embodiment of the present invention, in this step, aninorganic metal halide and an organic ammonium halide are dissolved in afirst solvent to obtain a precursor solution. Specifically, according toembodiments of the present invention, the first solvent includes one ormore selected from a group consisting of N,N-dimethyl formamide,dimethyl sulfoxide, tetrahydrofuran, acetonitrile, N-methylpyrrolidinone and acetone. Both the inorganic metal halide and theorganic ammonium halide exist in the first solvent in a dispersed form.It shall be noted that in the present invention, the expression“dispersed form” particularly means that both the inorganic metal halideand the organic ammonium halide are dispersed in the solution in freestates, with no coordination reaction occurring therebetween to resultin formation of any crystal or compound. Therefore, being able to selectan appropriate first solvent so that the inorganic metal halide andorganic ammonium halide are dissolved in the first solvent withoutcoordination reaction occurring between the metal cation and halogenanion, thereby obtaining a precursor solution where both the inorganicmetal halide and the organic ammonium halide are free and dispersive inthe precursor solution.

Further, according to an embodiment of the present invention, referringto FIG. 12, the precursor solution may be obtained by the followingsteps:

S110: mixing metal halide and organic ammonium halide

According to an embodiment of the present invention, in this step, onemetal selected from Ge, Sn, Ph, Si), Bi, Cu and Mn and one halogen ofchlorine, bromine and iodine form a metal halide, and the metal halideis mixed with an organic ammonium halide where the molar ratio of themetal halide to the organic ammonium halide is 1:(0.1˜3). Then, along-chain organic amine is added as the surface ligand to the mixtureof the metal halide and the organic ammonium halide, of which the molarratio of the long-chain organic amine to the inorganic metal halide is1:(0.1˜3). According to an embodiment of the present invention, themolecular formula of the long-chain organic amine may be RNH₂ in which Ris a saturated linear or a branched alkyl group or an unsaturated linearor a branched alkyl group. Selectively, according to an embodiment ofthe present invention, R may be an alkyl or aryl group containing from 4to 24 carbon atoms.

According to an embodiment of the present invention, the organicammonium halide is made as follows: dissolving an organic amine inabsolute ethanol to obtain a solution of which the volume of the organicamine accounts for 40%, and after stirring well, adding a haloid acid tothe solution in an ice water bath environment while stirring, the haloidacid includes one or more selected from a group consisting of HCl, HBrand HI, and the organic amine is a saturated alkyl amine that theformula is C_(n)H_(2n+1)NH₂ (n≥1) and an unsaturated alkyl or aryl aminethat its formula is C_(n)H_(2n−1)NH₂ (n≥2). According to an embodimentof the present invention, the molar ratio of the organic amine to thehaloid acid is 1:(1˜3). Specifically, according to an embodiment of thepresent invention, a mixture of the organic amine and the haloid acidmay be continuously stirred for 2 hours in the ice water bathenvironment, and then evaporated with a rotary evaporator at 50centigrade under a pressure −0.1 MPa to remove the solvent, and theremaining powder may be washed three times with diethyl ether, andfiltered to obtain a residue, and the residue may be dried in a vacuumdrying oven at 50 centigrade in the pressure of −0.1 MPa for 4 hours toobtain the organic ammonium halide.

S120: adding a first solvent

According to one embodiment of the present invention, in this step, anorganic acid is first added as the surface ligand to the mixture of theinorganic metal halide and the organic ammonium halide containing thelong-chain organic amine ligand, of which the molar ratio of the organicacid added to the inorganic metal halide is 0˜20:1, so as to obtain amixture solution containing the organic acid ligand. The organic acidsurface ligand may be a saturated or an unsaturated alkyl acid with atleast 3 carbon atoms. Specifically, according to one embodiment of thepresent invention, the organic acid may be a saturated alkyl acid thatits a formula is C_(n)H_(2n+1)COOH (n≥2), or an unsaturated alkyl acidthat its a formula is C_(n)H_(2n−1)COOH (n≥2). Then, a first solvent isadded to the mixture solution where the molar ratio of the first solventto the inorganic metal halide is (20˜1000):1.

According to another embodiment of the present invention, in this step,the molar ratio of the organic acid added to the inorganic metal halidemay also be 1:(0˜20), and the molar ratio of the first solvent added tothe inorganic metal halide may also be 1:(20˜1000). Thus, it is possibleto prepare quantum clot materials having different components and thusexpand the type of the quantum dot material prepared using this method,by adjusting the above-mentioned ratios.

S130: ultrasound.

According to an embodiment of the present invention, in this step,performing ultrasonic treatment to the mixture solution after adding thefirst solvent to it, then filtering via a 0.2 μm-pore size PTFE filterhead, retaining filtrate to obtain the precursor solution.

S200: obtaining quantum dot

According to an embodiment of the present invention, in this step, theprecursor solution is dropped into a second solvent, dropwise so thatthe inorganic metal halide and the organic ammonium halide in theprecursor solution are self-assembled to obtain a hybridized perovskitequantum dot material. Specifically, the second solvent includes one ormore selected from a group consisting of toluene, chloroform, n-hexane,cyclohexane, ethyl acetate and diethyl ether. Selectively, according tosome embodiments of the present invention, the second solvent and thefirst solvent are miscible. That means, being able to select a solventthat can be miscible with the first solvent as the second solvent tocomplete the preparation process of the quantum dot material. It shallbe noted that, in the present invention, the term “miscible”particularly means when the first solvent and the second solvent aremixed, no separation of layers occur in the mixed solution. Thus, it ispossible to select an appropriate organic matter from the above as thesecond solvent so that the solubility of the inorganic metal halide andthe organic ammonium halide in the first solvent is different from thatin the second solvent, thereby allowing the inorganic metal cation ofthe inorganic metal halide and halogen anions of the organic ammoniumhalide to form a coordination octahedral structure, allowing the organicammonium cations of the organic ammonium halide to enter into gaps ofthe coordinated octahedral structure simultaneously. A hybridizedperovskite quantum dot material having a relatively high fluorescencequantum yield and adjustable photoelectric properties may be madewithout using a template, therefore simplifying the process of makingthe quantum dot material.

According to an embodiment of the present invention, referring to FIG.13, after the precursor solution is prepared, the quantum dot materialcan be further obtained by the following steps:

S201: adding the second solvent

According to an embodiment of the present invention, the precursorsolution is added to the second solvent. Specifically, the precursorsolution is dropped into the second solvent at an adding speed of 10 μLto 1 mL per minute, dropwise while stirring. In this step, the volumeratio of the added precursor solution to the second solvent is1:(0.0001˜10). After finishing the dropping, the stirring iscontinuously performed for 2 hours to produce a suspension. Thus, theprecursor solution to the second solvent is added slowly to ensure thatthe coordination reaction of the inorganic metal cation of the inorganicmetal halide and the halogen anion of the organic ammonium halide isslow, so as to form a complete octahedral structure by self-assembly.

S220: Centrifuging

In this step, the solution obtained above is centrifuged. Specifically,according to an embodiment of the present invention, the centrifugingprocess may be performed with a centrifuge at a rotational speed of 7500rpm for 4 minutes. After the centrifuging, the hybridized perovskitequantum dot material is distributed in supernatant. Furthermore,inventors find that the precipitate after the centrifuging is hybridizedperovskite nanosheets or nanorods. Thus, the solution containing thequantum dot material may be simply separated from the other by-products,thereby decreasing the amount of impurities in the quantum dot materialmade by this method.

S230: distillation and drying

In this step, the above supernatant was distilled and dried to obtainthe quantum dot material according to an embodiment of the presentinvention. Specifically, according to an embodiment of the presentinvention, the supernatant is distilled, and after no liquid solvent isexisted, the remaining solid is dried for 8 hours at 70 centigrade undera pressure of −0.1 MPa to obtain the hybridized perovskite quantum dotmaterial. In this manner, a high purity quantum dot material can besimply obtained. Meanwhile, based on the method according to anembodiment of the present invention, the powdered quantum dot materialcan be obtained by drying process, while maintaining the quantum dotmaterial is stably existing without agglomeration.

Overall, in the second aspect of the present invention, the principle ofmaking the hybridized perovskite quantum dot material disclosed in thepresent invention is: both the inorganic metal halide and the organicammonium halide are soluble in the first solvent, and they exist thereinin a dispersed form to form a precursor solution. When the precursorsolution is dropped into the second solvent, dropwise, since thesolubility of the organic ammonium halide and the inorganic metal halidein the first solvent is different from that in the second solvent, theywill be fast self-assembled, an inorganic metal cation and halogenanions will form a coordination octahedral structure, and organicammonium cations will enter into gaps of the coordination octahedralstructure to form a hybridized perovskite structure; meanwhile, due tothe existence of the ligands such as organic acids, long-chain organicamines in the solution, these ligands will be wrapping out of thesurface of the formed regular octahedral particles to restrict thegrowth of the particles in three dimensions so as to keep the size ofthe particles in nano-scale, and finally forming the hybridizedperovskite quantum dots.

In the preparation method of the present invention, the hybridizedperovskite quantum dots having different luminescence wavelengths can bemade by adjusting amount ratio of the inorganic metal halide to thelong-chain organic amine; the hybridized perovskite quantum dots havingdifferent components can be made by adjusting variety and ratio of thefirst solvent to the second solvent; according to the preparation methodof the present invention, the surface ligand may be added to the firstsolvent or to the second solvent; the organic ligands are carried on thesurface of the hybridized perovskite fluorescence quantum dot and can bestably dispersed in the second solvent, which facilitates the processingand application of the hybridized perovskite fluorescence quantum dot,and the hybridized perovskite quantum dot material may be obtained byremoval of the organic solvents through distillation.

Therefore, the organic-inorganic hybridized perovskite fluorescencequantum dot material made by the aforementioned method has the followingadvantages:

1. The method provided in this invention for making the hybridizedperovskite quantum dot material requires no template and no heatingtreatment, own a rapid reaction, low cost and simple operations, and canget hybridized perovskite quantum dot powder and solutions of quantumdots dispersed in various organic solvents simultaneously.

2. The method can produce hybridized perovskite quantum dots having anultra-small particle size, and the quantum dot exhibits highluminescence intensity and its fluorescence quantum yield may be up to60%, which is much higher than that of the same kind material obtainedusing the conventional method.

3. The hybridized perovskite quantum dot material made by the methodprovided in the present invention can be stably dispersed in a varietyof organic solvents such as toluene, chloroform, n-hexane, cyclohexaneand ethyl acetate, and both the quantum dot powder and solution havinggood stability and fluorescence remains a long time without quenching,which sets up a good foundation for the application of the hybridizedperovskite quantum dot material.

4. The method is universal and can be applied to make a variety ofhybridized perovskite quantum dots, and by determining components andstructure of the hybridized perovskite material, quantum dots withdifferent luminescence wavelengths, which can cover the entire visibleregion, and have great advantages when applied to high color gamut whitelight LEDs.

5. By whole solution processing the hybridized perovskite quantum dotprepared in the present invention, a trans-electroluminescent devicehaving good performance can be obtained.

6. The hybridized perovskite quantum dot made in the present inventionhas a narrow half-peak width, emits high luminous purity, can meetrequirements in actual application, and owns a wide application prospectin fields of high-performance display devices, laser, non-linear optics,etc.

7. Hybridized perovskite nanosheets or nanorods can be also obtainedwhile obtaining hybridized perovskite quantum dots using the method ofthe present invention.

In a further aspect of the present invention, it provides a method forpreparing the hybridized perovskite quantum dot material as describedabove in the present invention. According to an embodiment of thepresent invention, the method includes the following steps:

(1) dissolving an organic amine in absolute ethanol to prepare asolution in which the volume of the organic amine is present accountsfor 40%, and stirring for 10 minutes until homogeneous; in an ice waterbath environment, adding a haloid acid to the solution where a molarratio of the organic amine to the haloid acid is 1:(1˜3) while stirring,and continuously stirring for 2 hours in the ice water bath environmentto obtain a clear solution; evaporating the solution with a rotaryevaporator at 50 centigrade under a pressure of −0.1 MPa to remove thesolvent and obtain crystalline powder of the organic ammonium halide;washing the crystalline powder three times with diethyl ether,filtering, and drying in a vacuum drying oven at 50 centigrade under apressure of −0.1 MPa for 4 hours to obtain the powder of the organicammonium halide. According to an embodiment of the present invention;the organic amine may be a saturated alkyl amine that its formula isC_(n)H_(2n+1)NH₂ (n≥1) or an unsaturated alkyl or aryl amine that itsformula of C_(n)H_(2n−1)NH₂ (n≥2).

(2) mixing the inorganic metal halide and the organic ammonium halidepowder at a molar ratio of 1:(0.1˜3), and then adding a long-chainorganic amine that the molar ratio of the long-chain organic amine tothe inorganic metal halide is 1:(0.1˜3). According to an embodiment ofthe present invention, the molecular formula of the long-chain organicamine may be RNH₂, of which R is a saturated linear or a branched alkylgroup or an unsaturated linear or a branched alkyl group. Specifically,according to some embodiments of the present invention, the long-chaingroup in the long-chain organic amine may be an alkyl or aryl grouphaving from 6 to 10 carbon atoms. Thereafter, an organic acid is addedwhere the molar ratio of the organic acid to the inorganic metal halideis 1:(0˜20), of which, the organic acid is a saturated or an unsaturatedalkyl acid with at least 3 carbon atoms, and according to an embodimentof the present invention, the organic acid may be a saturated alkyl acidthat its formula is C₂H_(2n+1)COOH (n≥2), or an unsaturated alkyl acidthat the formula is C_(n)H_(2n−1)COOH (n≥2). Then, a first solvent isadded where the molar ratio of the first solvent to the inorganic metalhalide is 1:(20˜1000) and mixed, performing ultrasonic treatment for 5minutes to obtain a clear mixed solution that then is filtered with a0.2 μm-pore size PTFE filter head to retain filtrate as a precursorsolution; in this step, the inorganic metal halide is one and only oneselected from a group consisting of halides of Ge, Sn, Pb, Sb, Bi, Cuand Mn, the halide includes one or more selected from a group consistingof chloride, bromide and iodide, and the first solvent is one and onlyone selected from a group consisting of N,N-dimethyl formamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile and acetone;

(3) placing a second solvent on a magnetic mixer to be fast stirred,dropping the precursor solution via a microsyringe at an adding speed of10 μL to 1 mL per minute to the second solvent, dropwise whilingstirring, where the volume ratio of the precursor solution to the secondsolvent is 1:(0.0001˜10), and continuously stirring for 2 hours toobtain a suspension of organic-inorganic hybridized perovskite material,of which the second solvent is one and only one selected from a groupconsisting of toluene, chloroform, n-hexane, cyclohexane, ethyl acetate,and diethyl ether;

(4) centrifuging the suspension of organic-inorganic hybridizedperovskite material obtained in step (3) with a centrifuge at arotational speed of 7500 rpm for 4 minutes to obtain precipitate that ishybridized perovskite nanosheets or nanorods and supernatant that is ahybridized perovskite quantum dot solution;

(5) distilling the hybridized perovskite quantum dot solution obtainedin step (4) to remove the organic solvents, and drying the remainingsolid in a vacuum drying oven at 70 centigrade under a pressure of −0.1MPa for 8 hours to obtain the hybridized perovskite quantum dotmaterial.

It is not difficult to see that simply obtaining the aforementionedhybridized perovskite quantum dot material in the present inventionusing the above method, and the quantum dot material made by this methodhas aforementioned properties and advantages of the above-mentionedquantum dot material, which will not be repeated here.

In a further aspect of the present invention, it discloses a hybridizedperovskite quantum dot material. According to an embodiment of thepresent invention, the hybridized perovskite quantum dot material ismade by the abovementioned method of the present invention. Thus, thehybridized perovskite quantum dot material has all properties andadvantages of the hybridized perovskite quantum dot material made by theabove-mentioned method.

In another aspect of the present invention, it discloses a method formaking perovskite quantum dot material. According to an embodiment ofthe present invention, the method includes:

(1) dissolving an inorganic metal halide and an organic ammonium halideor a halide of cesium in a first solvent to obtain a precursor solution,of which the inorganic metal halide and the organic ammonium halide orthe halide of cesium have good solubility in the first solvent, thusexist therein in a dispersed form.

Specifically, according to an embodiment of the present invention, theinorganic halide and the organic ammonium halide powders or halide of Csare mixed where the molar ratio of the inorganic halide to the organicammonium halide powder or the halide of Cs is 1:(0.1˜3). Then, along-chain organic amine is added as the surface ligand where the molarratio of the long-chain organic amine to the inorganic metal halide is1:(0.1˜3). The molecular formula of the long-chain organic amine is RNH₂of which R represents a saturated linear or a branched alkyl group or anunsaturated linear or a branched alkyl group, Selectively, the R groupin the long-chain organic amine may be an alkyl or aryl group havingfrom 4 to 24 carbon atoms. Thereafter, an organic acid is added to themixture of the inorganic halide mixed with the organic ammonium halidepowders or the halide of Cs containing the long-chain organic amine, ofwhich, the organic acid is used as the surface ligand where the molarratio of the organic acid to the inorganic halide may be (0˜100):(1˜10).According to an embodiment of the present invention, the organic acidmay be a saturated alkyl acid that its formula is C_(n)H_(2n+1)COOH(n≥2), or an unsaturated alkyl acid that its formula isC_(n)H_(2n−1)COOH (n≥2). Finally, a first solvent is added to themixture containing the organic acid and the long-chain organic amine.The molar ratio of the added first solvent to the inorganic halide maybe (20˜1000):(1˜10). After mixing, performing ultrasonic treatment tothe mixture for 5 minutes to obtain a transparent solution, subsequentlyfiltering the transparent solution with a 0.2 μm-pore size PTFE filterhead, retaining filtrate to obtain the precursor solution. According toan embodiment of the present invention, the inorganic halide in thisstep is any of halides of Ge, Sn, Pb, Sb, Bi, Cu, and Mn; and the firstsolvent is one or more selected from a group consisting of N,N-dimethylformamide, acetonitrile, N-methyl pyrrolidinone and dimethyl sulfoxide.

According to an embodiment of the present invention, the organicammonium halide added in this step is made by the following steps:dissolving an organic amine in absolute ethanol and mixing them well bystirring to produce a solution, of which the volume of the organic amineaccounts for 40%, the organic amine is one and only one selected from agroup consisting of methylamine, formamide, and acetamine. In an icewater bath environment, the haloid acid is added to the obtainedsolution where the molar ratio of the added haloid acid to the organicamine is (1˜3):1. The mixture containing the haloid acid is continuouslystirred in the ice water bath environment for 2 hours to obtain a clearsolution, then evaporating the clear solution with a rotary evaporatorat 50 centigrade under a pressure −0.1 MPa to remove the solvent andobtain crystalline powder of the organic ammonium halide. Thecrystalline powder is washed with diethyl ether several times, filteredand dried in a vacuum drying oven at 50 centigrade under a pressure −0.1MPa for 4 hours to obtain the organic ammonium halide powder.

(2) In this step, the precursor solution obtained in step (1) is addedto a second solvent to form an emulsion system. Specifically, theemulsion system is obtained by the following steps:

According to an embodiment of the present invention, the second solventis placed on a magnetic mixer to be fast stirred, and the precursorsolution is added to the second solvent, dropwise while stirring, ofwhich the second solvent is one or more selected from a group consistingof 1-octadecene (ODE), n-hexane, cyclohexane and n-heptane, and thesecond solvent selected in this step is immiscible with the firstsolvent in step (1). It shall be noted that the term “immiscible” in thepresent invention particularly means that, when the first solvent andthe second solvent are mixed, separation of layers occur in the mixedsolution. Thus, an emulsion system may be simply formed by selecting twokinds of immiscible solvents as the first solvent and the secondsolvent, respectively.

Furthermore, according to an embodiment of the present invention, theprecursor solution is added at an adding speed of 10 μL to 1 mL perminute, and the volume ratio of the added precursor solution to thesecond solvent is 1:(0.0001˜10). According to an embodiment of thepresent invention, slowly dropping the precursor solution in a smallamount is conducive to obtain the emulsion system. Thus, the precursorsolution can be dropped via a microsyringe. After adding the precursorsolution, the mixed solution is continuously stirred for 2 hours toobtain the emulsion system of the perovskite material.

(3) A demulsifier is added to the emulsion system so that the inorganicmetal halide and the organic ammonium halide or the halide of cesium areself-assembled to obtain a perovskite quantum dot material.Specifically, according to an embodiment of the present invention, thedemulsifier is added to the emulsion system of the perovskite materialwhere the added volume ratio of the demulsifier to the second solvent is1:(1˜10). Thereafter, the emulsion system in which the demulsifier hasbeen added is centrifuged by use of a centrifuge at a rotational speedof 7500 rpm for 4 minutes. After the centrifuging, supernatant isretained to obtain a perovskite quantum dot solution. Finally, theperovskite quantum dot solution is washed to remove the organic solvent.The solution from which the organic solvent has been removed is driedunder vacuum to obtain powder, the power is the perovskite quantum dotmaterial powder. According to an embodiment of the present invention,the demulsifier may be one or more selected from a group consisting ofacetone, methanol, isopropanol, n-butanol and tert-butanol. Thus, purequantum dot powder may be directly obtained using this method, and thequantum dot material in the powder can stably exist and not agglomerate,which enables the quantum dot material to be applied in more extensivefields

Furthermore, by adjusting the amount of the demulsifier added in thisstep, being able to obtain products such as nanorods and nanosheetswhile obtaining the powdered quantum dot material. According to anembodiment of the present invention, when the volume ratio of the addeddemulsifier to the second solvent is 1:(5˜20), a solution containing thenanorods and quantum dot material can be obtained. Powdered quantum dotmaterial and nanorods can be obtained respectively by centrifuging in alater stage. When the volume ratio of the added demulsifier to thesecond solvent is 1:(1˜5), a solution containing nanosheets, nanorodsand the quantum dot material can be obtained. Therefore, a variety ofperovskite materials with different morphologies may be obtained whileobtaining the quantum dot material.

To be understood easily, the principle of making the perovskite quantumdot material via this method will be explained hereinafter: both theinorganic metal halide and the organic ammonium halide or the halide ofcesium are soluble in the first solvent, they can exist therein in adispersed form. In other words, there is no coordination reaction of theinorganic metal halide and the organic ammonium halide or the halide ofcesium to cause a crystal nucleus or compound in the first solvent. Whenthe precursor solution is added to the second solvent, since the firstsolvent contained in the precursor solution and the second solvent areimmiscible, and the organic amine and organic acid added as surfaceligands in advance into the first solvent and the second solvent areamphiphilic, the organic amine and organic acid can encapsulate theprecursor solution containing the first solvent to form micelles. Theprecursor solution is encapsulated in the micelles, which may form smalldroplets and be dispersed in the second solvent, then form an emulsionsystem; after adding the demulsifier, a balance emulsion system isdestroyed and the precursors in the small droplets are diffused into thesecond solvent and fast self-assembled to form perovskite crystalnucleus. Meanwhile, due to hydrogen bonds between the micelles withoutbeing destroyed and the perovskite crystal nucleus in the emulsion, themicelles are adsorbed on the surface of the crystal nucleus working assurface ligands to restrict the growth of the crystal nucleus andfinally keep the size of the particles in nano-scale.

Furthermore, the perovskite quantum dot material made by the method ofthe present invention has aforementioned properties and advantages ofthe perovskite quantum dot material, and will not be repeated here.

In another aspect of the present invention, it discloses a semiconductordevice. According to an embodiment of the present invention, thesemiconductor device includes the aforementioned perovskite quantum dotmaterial according to any embodiments of the present invention. Sincethe semiconductor device includes the quantum dot material, thesemiconductor device has aforementioned properties and advantages of thequantum dot material, which will not be repeated here. Therefore, thequantum dot material is made at a corresponding position of thesemiconductor device, which may improve effect of use of the device.

According to an embodiment of the present invention, the semiconductormay be electroluminescent devices, solar batteries, display devices andnon-linear optical devices. Thus, the aforementioned quantum dotmaterial can be applied to these devices to perform the aforementionedproperties and advantages, thereby being able to improve the use effectof these devices.

It shall be noted that, the described properties and effects can bemutually applied to all aspects of the present invention, which will notbe repeated here.

The present invention will be explained below through specificembodiments, and it shall be noted that the following specificembodiments are merely for illustrative purpose, and not to limit thescope of the present invention by any means. In addition, unlessparticularly stated, methods without giving specific conditions or stepsare conventional methods, and reagents and materials adopted arecommercially available.

Embodiment 1

This embodiment adopted oleic acid and 2-ethylhexylamine as surfaceligands for making CH₃NH₃PbI₃ quantum dot, the following detailed stepsare hereinafter:

(1) Preparation of Methylammonium Iodide

5 mL a solution of 30% (mass percent) methylamine in ethanol (degree ofpurity>99.9%) was measured with a 10 mL transfer pipette, placed in a100 mL round-bottomed flask and continuously stirred for 10 minutesuntil homogeneous. In an ice water bath environment, 5 mL 57% (masspercent) hydroiodic acid was added to the obtained solution whilestirred, and then continuously stirred in the ice water bath environmentfor 2 hours to obtain a clear solution, and the solution was distilledwith a rotary evaporator at 50 centigrade under a reduced pressure of−0.1 MPa to remove the solvent. After the rotary distillation, theremain in the round-bottomed flask was washed with anhydrous diethylether three times, to which air pump filtration is performed and driedin a vacuum drying oven at 50 centigrade under a pressure of −0.1 MPafor 4 hours to obtain methylammonium iodide powders;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol methylammonium iodide and 0.2mmol lead iodide, and 40 μL 2-ethylhexylamine via a microsyringe, 1 mLoleic acid via a dropper and 10 mL acetone were added thereto, to whichultrasonic treatment is performed for 5 minutes to obtain a clear andtransparent yellowish-brown solution, which was then filtered with a 0.2μm-pore size PATE filter head to obtain clear filtrate as a precursorsolution before reaction.

(3) Removal of Oxygen from the Precursor Solution and a Second Solvent

Another 10 mL isotope vial was taken, and 10 mL toluene was addedthereto. Air in the precursor solution and in n-hexane was drained awayvia nitrogen provided with a needle, and the precursor solution andtoluene were then transferred to a glove box for next operation;

(4) Mixing of the Precursor Solution and the Second Solvent

Toluene in step (3) was placed on a magnetic mixer to be fast stirred,and the precursor solution was extracted via a microsyringe and droppeddropwise into n-hexane while being fast stirred, where one drop (about10 μL) is added every 30 seconds, until that 300 μL precursor solutionwas added, while monitored by an ultraviolet lamp. It can be observedthat the solution of CH₃NH₃PbI₃ quantum dots was brown and emitted dimrose-carmine light under the ultraviolet lamp. Luminescence measuredwith fluorescence spectrometer of the quantum dot covered the nearinfrared region where the luminescence peak appeared at 726 nm. FIG. 2was the fluorescence spectrogram of the obtained CH₃NH₃PbI₃ quantum dot.

In this embodiment, if 60 μL the 2-ethylhexylamine was added, theobtained quantum dot would have a luminescence wavelength of 740 nm, andif 20 μL the 2-ethylhexylamine was added, the obtained quantum dot wouldhave a luminescence wavelength at 700 nm. That is, different ratios ofthe inorganic metal halide to the long-chain organic amine causedhybridized perovskite quantum dots having different luminescencewavelengths.

Embodiment 2

This embodiment adopted butyric acid and octadecylamine as surfaceligands for preparing CH₃NH₃PbCl₃ quantum dot by the following specificsteps:

(1) Preparation of Methylammonium Chloride

5 mL a methylamine in ethanol solution (degree of purity >999%) that itsmass percent is 30% was measured via a 10 mL transfer pipette, placed ina 100 mL round-bottomed flask and stirred for 10 minutes untilhomogeneous. In an ice water bath environment, 5 mL 37% (mass percent)concentrated hydrochloric acid was added to the obtained solution whilestirred, and then continuously stirred in the ice water bath environmentfor 2 hours to obtain a clear solution, and the solution was evaporatedwith a rotary evaporator at 50 centigrade under a pressure of −0.1 MPato remove the solvent. The remain in the round-bottomed flask was washedwith anhydrous diethyl ether three times, to which air pump filtrationis performed and dried in a vacuum drying oven at 50 centigrade under apressure of −0.1 MPa for 4 hours to obtain methylammonium chloridepowder;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, and to the vial was added 0.2 mmolmethylammonium chloride, 0.2 mmol lead chloride, 0.4 mmoloctadecylamine, 1 mL butyric acid using a dropper and 10 mL dimethylsulfoxide, and performing ultrasonic treatment for 5 minutes to obtain aclear transparent colorless solution, which was then filtered with a 0.2arm-pore size PTFE filter head to obtain clear filtrate as a precursorsolution before reaction;

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL chloroform was thenadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn by a microsyringe and dropped dropwiseinto chloroform which was being fast stirred in step (3), of which onedrop (about 10 μL) is added every 30 seconds, until that 1 mL theprecursor solution was added, while monitored with the ultraviolet lamp.It could be observed that the solution of CH₃NH₃PbCl₃ quantum dot inchloroform was light blue and emitting purple light under irradiation ofthe ultraviolet lamp. Luminescence measured via a fluorescencespectrometer, of the quantum dot covered the violet region withluminescence peak appearing at 406 nm.

(5) Obtaining Quantum Dot Powder

The quantum dot solution obtained in step (4) was transferred to adistillation flask and distilled with a vacuum distillation unit toremove the organic solvents, and the remaining solid was dried in avacuum drying oven for 8 hours to obtain crystalline powder ofCH₃NH₃PbCl₃ quantum dots that were white.

Embodiment 3

This embodiment adopted propionic acid and n-hexylamine as surfaceligands for preparing CH₃NH₃PbBr₃ quantum dot by the following specificsteps:

(1) Preparation of Methylammonium Bromide

5 mL a solution of 30% (mass percent) methylamine in ethanol (degree ofpurity>99.9%) was measured with a 10 mL transfer pipette, placed in a100 mL round-bottomed flask and stirred for 10 minutes untilhomogeneous. In an ice water bath environment, 5 mL 49% (mass percent)hydrobromic acid was added to the obtained solution while stirred, andthen continuously stirred in the ice water bath environment for 2 hoursto obtain a clear solution, and the solution was distilled with a rotaryevaporator at 50 centigrade under a reduced pressure of −0.1 MPa toremove the solvent. The remain in the round-bottomed flask was washedwith anhydrous diethyl ether three times, to which the air pumpfiltration is performed and dried in a vacuum drying oven at 50centigrade under a pressure of −0.1 MPa for 4 hours to obtainmethylammonium bromide powder;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol methylammonium bromide and 0.2mmol lead bromide, and then 0.4 mmol n-hexylamine, 1 mL propionic acidvia a dropper and 10 mL N,N-dimethyl formamide were added thereto, towhich ultrasonic treatment is performed for 5 minutes to obtain a cleartransparent solution, which was then filtered with a 0.2 μm-pore sizePTFE filter head to obtain clear filtrate as a precursor solution beforereaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL toluene was thenadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn using a microsyringe and droppeddropwise into toluene which was being fast stirred in step (3), of whichone drop (about 10 μL) is added every 30 seconds, until that 1 mL theprecursor solution was added, while monitored with the ultraviolet lamp.It could be observed that yellowish-brown turbidity appeared in thetoluene solution and the solution exhibited green color under theultraviolet lamp;

(5) Post-Treatment of the Quantum Dot Solution

The quantum dot solution obtained in step (4) was transferred to acentrifuge tube to be centrifuged at 7500 rpm for 10 minutes, and itcould be observed that the upper layer is a bright green solution, andthe lower layer is dark yellow precipitate. The supernatant was drawnout to obtain the solution of CH₃NH₃PbBr₃ quantum dots. FIG. 3 is imagesof the obtained CH₃NH₃PbBr₃ quantum dots under a fluorescent lamp andthe ultraviolet lamp; FIG. 4 is an absorption spectrum and an emissionspectrum of the quantum dot, and shows luminescence peak of the quantumdot at 515 nm. The precipitate is hybridized perovskite nanosheets ornanorods, and FIG. 5 is a scanning electron microscopy image of theprecipitate.

(6) Obtaining Quantum Dot Powder

The bright green supernatant obtained in step (4) was transferred to adistillation flask and distilled with a vacuum distillation unit toremove the organic solvents, and the remaining solid was dried in avacuum drying oven for 8 hours to obtain crystalline powder ofCH₃NH₃PbBr₃ quantum dots, which was yellowish-green. FIG. 6 is atransmission electron microscopy image of the quantum dots.

In step (2) of this embodiment, if the surface ligands (n-hexylamine andpropionic acid) are not added to the first solvent, but to the secondsolvent in step (3), a hybridized perovskite quantum dot material can bealso obtained.

Embodiment 4

This embodiment adopted n-octylamine as a surface ligand for preparing(C₂H₅NH₃)₂GeI₄ quantum dot by the following specific steps:

(1) Preparation of Ethylammonium Iodide

5 mL ethylamine (degree of purity>99.9%) was measured with a 10 mLtransfer pipette, diluted with absolute ethanol into a solution wherethe volume percentage of ethylamine was 40%, and placed in a 100 mLround-bottomed flask and stirred for 10 minutes until homogeneous. In anice water bath environment, 5 mL 49% (mass percent) hydroiodic acid wasadded to the obtained solution while stirred, and then continuouslystirred in the ice water bath environment for 2 hours to obtain a clearsolution. The solution was distilled with a rotary evaporator at 50centigrade under a reduced pressure −0.1 MPa to remove the solvent. Theremain in the round-bottomed flask was washed with anhydrous diethylether three times, to which the air pump filtration is performed anddried in a vacuum drying oven at 50 centigrade under a pressure of −0.1MPa for 4 hours to obtain ethylammonium iodide powder;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol ethylammonium iodide and 0.2mmol germanium iodide, 40 μL n-octylamine via, a microsyringe and 10 mLacetonitrile via a dropper were added thereto, and to which ultrasonictreatment is performed for 5 minutes to obtain a, clear transparentsolution, which was then filtered with a 0.2 μm-pore size PTFE filterhead to obtain clear filtrate as a precursor solution before reaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 frit diethyl ether wasthen added, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn using a microsyringe and droppeddropwise into diethyl ether which was being fast stirred in step (3), ofwhich one drop (about 10 μL) is added every 5 seconds, until 2 mL theprecursor solution was added. It could be observed that turbidityappeared in the solution.

(5) Centrifuging to Obtain a Clear Solution

The solution obtained in step (4) was transferred to a centrifuge tubeto be centrifuged at 7000 rpm for 4 minutes, and supernatant was drawnout by a dropper, which was an ink black solution with luminescence inthe infrared region.

Embodiment 5

This embodiment adopted oleyl amine and n-hexylamine as surface ligandsfor making CH₃NH₃PbCl_(x)Br_(3−x) (0≤x≤3) quantum dots by the followingsteps:

(1) Preparation of Methylammonium Chloride

A 10 mL isotope vial was taken, and to the vial, added 0.2 mmolmethylammonium chloride, 0.2 mmol lead bromide, 40 μL n-hexylamine byuse of a microsyringe, 1 mL oleyl amine by use of a dropper and 10 mLN,N-dimethyl formamide, to which ultrasonic treatment is performed for 5minutes to obtain a clear transparent solution that was then filteredwith a 0.2 μm-pore size PTFE filter head to obtain clear filtrate as aprecursor solution before reaction;

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL chloroform was thenadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn by use of a microsyringe and added tochloroform, dropwise, that was being fast stirred in step (3), of whichone drop (about 10 μL) is added every 10 seconds, until 1 mL theprecursor solution was added. It could be observed that the solutionbecame turbid gradually and greenish particles were produced;

(5) Centrifuging

The turbid solution obtained in step (4) was transferred to a centrifugetube and centrifuged at 7500 rpm for 10 minutes to result in light bluesupernatant and cyan precipitate. The supernatant exhibited blue colorunder irradiation of an ultraviolet lamp. FIG. 7 shows images of thequantum dot solution under the fluorescent and ultraviolet lamps; FIG. 8shows emission spectrum of the quantum dots.

Embodiment 6

This embodiment adopted oleic acid and n-octylamine as surface ligandsfor making CH₃NH₃PbI_(x)Br_(3−x) (0≤x≤3) quantum dots by the followingsteps:

(1) Preparation of Methylammonium Bromide

The preparation method of methylammonium bromide was the same as thatdescribed in step (1) of embodiment 3;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, and to the vial, added 0.2 mmolmethylammonium bromide, 0.2 mmol lead iodide, 40 μL n-octylamine by useof a microsyringe, 1 mL oleic acid by use of a dropper and 10 mLtetrahydrofuran (THF), to which ultrasonic treatment is performed for 5minutes to obtain a clear transparent light yellow solution that wasthen filtered with a 0.2 μm-pore size PTFE filter head to obtain clearfiltrate as a precursor solution before reaction;

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL cyclohexane wasthen added, then placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn using a microsyringe and added to thecyclohexane dropwise which was being fast stirred in step (3), of whichone drop (about 10 μL) is added every 5 seconds, and upon 100 μL theprecursor solution was added, continuously stirred for 5 minutes, andthen added another 100 μL the precursor solution, repeated until 1 mLthe precursor solution was added into. It could be observed that thesolution of the CH₃NH₃PbI_(x)Br_(3−x) quantum dots was black red,emitting dark red light under the ultraviolet lamp and measured via aspectrometer that a luminescence peak is at 650 nm.

(5) Obtaining the Quantum Dot Powder

The black red quantum dot solution obtained in step (4) was transferredto a distillation flask, and distilled via a vacuum distillation unit toremove the organic solvents and obtain crystalline powder of theCH₃NH₃PbI_(x)Br_(3−x) quantum dots, which is black red powder;

(6) Encapsulating the Quantum Dot Powder

The quantum dot powder obtained in step (5) was re-dissolved in toluene.An amount of PMMA was measured and added to a solution of quantum dotsin cyclohexane so that the mass percent of the PMMA in the solution was5%. The mixed solution was equally spread on a watchglass and placed ina fume cupboard. After cyclohexane was completely volatilized, shapedPMMA film was taken off the watchglass to obtain a composite film of thequantum dots and PMMA, which was dark red.

Embodiment 7

This embodiment adopted hexanoic acid and laurylamine as surface ligandsfor making CH₃NH₃SnI₃ quantum dot by the following steps:

(1) Preparation of Methylammonium Iodide

The method of making methylammonium iodide was the same as thatdescribed in step (1) of Embodiment 1;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, and to the vial was added 0.2 mmolmethylammonium iodide, 0.2 mmol stannic iodide, 40 μL laurylamine by useof a microsyringe, 1 mL hexanoic acid via a dropper and 10 mLN,N-dimethyl formamide, to which ultrasonic treatment was performed for5 minutes to obtain a clear transparent solution, which was thenfiltered a 0.2 μm-pore size PTFE filter head to obtain clear filtrate asa precursor solution before reaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL cyclohexane wasadded for next operation:

(4) Removal of Oxygen from the Precursor Solution and the Second Solvent

Isotope vials containing the precursor solution and the second solventwere respectively sealed via a rubber plug, and oxygen in the precursorsolution and the second solvent was drained away via nitrogen, then theprecursor solution and the second solvent were transferred to a glovebox;

(5) Preparation of a Quantum Dot Solution

Cyclohexane in which oxygen had been drained away in step (4) was placedon a magnetic mixer to be fast stirred, and the precursor solution wasdrawn by a microsyringe and added to cyclohexane dropwise which wasbeing fast stirred, of which one drop (about 10 μL) is added every 30seconds, until 100 μL the precursor solution was added. It could beobserved that obtained solution of CH₃NH₃SnI₃ was black.

Embodiment 8

This embodiment adopted oleic acid as a surface ligand for making(C₆H₅NH₃)₂PbI₄ quantum dot by the following steps:

(1) Preparation of Phenylethylammonium Iodide

5 mL phenylethylamine was measured by a 10 mL transfer pipette andplaced in a 100 mL round-bottomed flask, then 7.5 mL absolute ethanolwas added thereto, to dilute it into a solution of 40% (volume percent)phenylethylamine in ethanol. The solution was stirred for 10 minutesuntil homogeneous. In an ice water bath environment, 4 mL 57% (masspercent) hydroiodic acid was added to it while stirred, and continuouslystirred in the ice water bath environment for 2 hours to obtain a clearsolution, evaporated the solution with a rotary evaporator at 50centigrade under a pressure of −0.1 MPa to remove the solvent and toobtain crystalline the phenylethylammonium powder

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, then to the vial, 0.2 mmolphenylethylammonium iodide, 0.2 mmol lead iodide, 1 mL oleic acid via adropper and 10 mL N,N-dimethyl formamide were added, to which ultrasonictreatment is performed for 5 minutes to obtain a clear transparent mixedsolution that was then filtered with a 0.2 μm-pore size PTFE filter headto obtain clear filtrate as a precursor solution before reaction;

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL chloroform wasadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn via a microsyringe and added tochloroform dropwise which was being fast stirred in step (3), of whichone drop (about 10 μL) is added every 5 seconds, until that 0.5 mL theprecursor solution was added. It could be observed that the obtainedchloroformic solution of (C₆H₅NH₃)₂PbI₄ quantum dots is light yellow,the luminescence peak of the quantum dots is at 530 nm. FIG. 9 is theemission spectrum of the quantum dots.

Embodiment 9

This embodiment adopted decoic acid as a surface ligand for makingCH₃NH₃CuBr₃ quantum dot by the following steps:

(1) Preparation of Methylammonium Bromide

The method for making methylammonium bromide was the same as thatdescribed in step (1) of Example 3;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, then to the vial, 0.2 mmolmethylammonium bromide and 0.2 mmol copper bromide, 1 mL decoic acid viaa microsyringe and 10 mL N,N-dimethyl formamide were added, to whichultrasonic treatment is performed for 5 minutes to obtain a cleartransparent mixed solution that was then filtered via a 0.2 μm-pore sizePTFE filter head to obtain clear filtrate as a precursor solution beforereaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL toluene was added,and placed on a magnetic mixer to be fast stirred for next operation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn via a microsyringe and added to toluenedropwise which was being fast stirred in step (3), of which one drop isadded every 30 seconds, until that 0.5 mL the precursor solution wasadded. It could be observed that the obtained toluene solution ofCH₃NH₃CuBr₃ quantum dots exhibit the color of dark purple.

Embodiment 10

This embodiment adopted pentanoic acid and 3-vinythexylamine as surfaceligands for making (C₆H₅NH₃)₂BiCl₄ quantum dot by the following steps:

(1) Preparation of Phenylethylammonium Iodide

The method for making phenylethylammonium iodide was the same as thatdescribed in step (1) of embodiment 8.

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, to the vial, 0.2 mmolphenylethylammonium iodide, 0.2 mmol bismuth chloride, 1 ml pentanoicacid via a dropper, 40 μL 3-vinylhexylamine and 10 mL DMSO were added,to which ultrasonic treatment was performed for 5 minutes to obtain aclear transparent mixed solution that was then filtered with a 0.2μm-pore size PTFE filter head to obtain clear filtrate as a precursorsolution before reaction;

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL cyclohexane wasadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn via a microsyringe and added tocyclohexane dropwise which was being fast stirred in step (3), of whichone drop is added every 5 seconds, until that 0.5 mL the precursorsolution was added. It could be observed that the obtained solution of(C₆H₅NH₃)₂BiCl₄ quantum dots was colorless.

Embodiment 11

This embodiment adopted octanoic acid and hexadecylamine as surfaceligands for making CH₃NH₃MnI₃ quantum dot by the following steps:

(1) Preparation of Methylammonium Iodide

The method for making methylammonium iodide was the same as thatdescribed in step (1) of Example 1;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, and to the vial, 0.2 mmol methylammoniumiodide, 0.2 mmol manganese iodide, 1 mL octanoic acid via a dropper, 40μL hexadecylamine and 10 mL acetone were added, to which ultrasonictreatment is performed for 5 minutes to obtain a clear transparent mixedsolution that was then filtered with a 0.2 μm-pore size PTFE filter headto obtain clear filtrate as a precursor solution before reaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL cyclohexane wasadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn via a microsyringe and added tocyclohexane dropwise which was being fast stirred in step (3), of whichone drop is added every 5 seconds until that 0.5 ml the precursorsolution was added. It could be observed that the obtained solution ofCH₃NH₃MnI₃ quantum dots was purple-black.

Embodiment 12

This embodiment adopted butylamine as a surface ligand for makingCH₃NH₃SbCl₃ quantum dot by the following steps:

(1) Preparation of Methylammonium Chloride

The method for making methylammonium chloride was the same as thatdescribed in step (1) of Embodiment 2.

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, and to the vial, 0.2 mmol methylammoniumchloride, 0.2 mmol antimony chloride, 40 μL octylamine using a dropperand 10 mL acetone were added, to which ultrasonic treatment is performedfor 5 minutes to obtain a clear transparent mixed solution that was thenfiltered with a 0.2 μm-pore size PTFE filter head to obtain clearfiltrate as a precursor solution before reaction;

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL n-hexane was added,and placed on a magnetic mixer to be fast stirred for next operation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn via a microsyringe and added ton-hexane dropwise which was being fast stirred in step (3), of which onedrop is added every 5 seconds until that 0.5 mL the precursor solutionwas added. It could be observed that the obtained solution ofCH₃NH₃SbCl₃ quantum dots was colorless.

Embodiment 13

This embodiment adopted 2-butyl tetradecyl amine as a surface ligand formaking (CH₂═CHCH₂CH₃NH₃)₂SnI₄ quantum dot by the following steps:

(1) Preparation of 3-Butenyl-1-Ammonium Iodide

The method for making 3-butenyl-1-ammonium iodide was the same as thatdescribed in step (1) of embodiment 4, except that ethylamine in step(1) was replaced with 4-amino-1-butene;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, and to the vial was added 0.2 mmol3-butenyl-1-ammonium iodide, 0.2 mmol stannic iodide, 40 μL 2-butyltetradecyl amine via a dropper and 10 mL THF, to which ultrasonictreatment was performed for 5 minutes to obtain a clear transparentlight red mixed solution that was then filtered with a 0.2 μm-pore sizePTFE filter head to obtain clear filtrate as a precursor solution beforereaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL chloroform wasadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of a Quantum Dot Solution

The precursor solution was drawn via a microsyringe and added tochloroform dropwise which was being fast stirred in step (3), of whichone drop is added every 5 seconds until that 0.5 mL the precursorsolution was added. It could be observed that the obtained solution of(CH₂═CHCH₂CH₃NH₃)₂SnI₄ quantum dots was red.

Embodiment 14

This embodiment was based on obtained CH₃NH₃PbBr₃ quantum dots toconstruct a trans-electroluminescent device by the following steps:

(1) Preparation of a ITO (Indium Tin Oxide) Conductive Glass Substrate

The ITO conductive glass was cut into square bases with a size of2.5*2.5 cm², washed with deionized water and then put into acetone andisopropanol for the ultrasonic treatment for 15 minutes successively,and the cleaned ITO conductive glasses were soaked in isopropanol forusage;

(2) Preparation of Spin-Coating Solution

Two isopropoxide dual ancetylacetone ti (abbreviated to ‘TlPD’) wasdissolved in isopropanol to prepare a spin-coating solution for theelectron transport layer material, of which the mass percent of TIPD was25%; dissolving the prepared hybridized perovskite quantum dots of whichconcentration is maintained at 10 mg/mL into the toluene, to prepare aspin-coating solution for the quantum dot layer;poly(bis(4-phenyl)(4-butylphenyl)amine) (abbreviated to ‘poly-TPD’)powder was dissolved in chlorobenzene to form a spin-coating solutionfor the hole transport material, of which the mass percent of poly-TPDis 10%. The above spin-coating solutions were respectively filtered viaa 0.22 μm filter head then the filtrates were transferred to samplebottles for usage;

(3) Spin-Coating

The obtained ITO conductive glass was taken out and placed on a rotaryplate of a spin coater. The spin-coating solution of TIPD in isopropanolwas drawn via a microsyringe and dropped on the ITO surface to uniformlycover the ITO surface that was then spin-coated at 2000 rpm for 30seconds. In the same way, the quantum dot layer and the hole transportlayer (poly-TPD) were spin-coated successively, and the method forspin-coating them was the same as that mentioned above. Every time thespin-coating was finished, the ITO was placed on a hot platform to bequenched at 70 centigrade for 15 minutes;

(4) Deposition Electrode

A layer of Al electrode with a thickness of 100 nm was deposited via avacuum coating instrument on the poly-TPD hole transport layer. FIG. 10is a structural schematic view of the constructed electroluminescencedevice. A voltage was applied across the electrode and it could beobserved that the device emitted bright green light, and the intensityof the light was gradually increasing along with increasing of thevoltage.

Embodiment 15

This embodiment adopted n-octylamine as a surface ligand for pmakingCsPbBr3 quantum dot by the following steps:

(1) Preparation of Cesium Oleate

A 100 mL three-necked flask was taken and 2.5 mmol cesium carbonate, 30ml octadecene via a graduated cylinder and 2.5 mL oleic acid via adropper were added thereto, heated to 120 centigrade, being in vacuumfor reaction for 1 hours, then warmed up to 150 centigrade until thatthe cesium carbonate was completely dissolved to get a brown solution,and to take a clear solution as a precursor solution before reaction.

(2) Preparation of Lead Bromide Solution

Another 5 mL isotope vial was taken, 0.38 mmol lead bromide and 0.6 mLof N,N-dimethyl formamide via a dropper were added thereto, to whichultrasonic treatment was performed for 5 minutes to obtain a cleartransparent solution.

(3) Preparation of a Second Solvent

A 30 mL isotope vial was taken, 10 mL n-hexane, 2 mL oleic acid, 0.5 mLn-octylamine, 0.4 mL cesium oleate precursor solution made in step (1)and 0.2 mL N,N-dimethyl formamide were added thereto, the vial wasplaced on a magnetic mixer to be fast stirred for next operation:

(4) Preparation of a Quantum Dot Solution

The lead bromide solution was drawn via a microsyringe and added to thesolution dropwise which was being fast stirred in step (3), of which onedrop (about 10 μL) is added every 10 seconds until that the precursorsolution was completely added. 8 mL acetone was added via a dropper, andit was observed that the solution gradually became turbid and yellowishgreen particles were formed;

(5) Centrifuging

The turbid solution obtained in step (4) was transferred to a centrifugetube and centrifuged at 7000 rpm for 10 minutes to get a colorlesssupernatant and yellowish green precipitate. The precipitate presentedblue color under irradiation of the ultraviolet lamp. The precipitatewas dissolved in n-hexane to obtain the quantum dot solution.

Embodiment 16

This embodiment adopted n-hexylamine as a surface ligand, N,N-dimethylformamide as the first solvent, and n-hexane as the second solvent formaking CH₃NH₃PbBr₃ quantum dot by the following steps:

(1) Preparation of Methylammonium Bromide

5 mL a solution of 30% (mass percent) methylamine in ethanol (degree ofpurity>99.9%) was measured via a 10 mL transfer pipette, placed in a 100mL round-bottomed flask and stirred for 10 minutes until homogeneous. Inan ice water bath environment, 5 mL 49% (mass percent) hydrobromic acidwas added to the obtained stirred solution then which is continuouslystirred in the ice water bath environment for 2 hours to obtain a clearsolution, and the solution was distilled with a rotary evaporator at 50centigrade under a reduced pressure of −0.1 MPa to remove the solvent.The remain in the round-bottomed flask was washed with anhydrous diethylether three times, to which air pump filtration is performed and driedin a vacuum drying oven at 50 centigrade under a pressure of −0.1 MPafor 4 hours to obtain powder of methylammonium bromide;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol methylammonium bromide, 0.2mmol lead bromide, 0.4 mmol n-hexylamine, 1 mL propionic acid via adropper and 1 mL N,N-dimethyl formamide were added thereto, to whichultrasonic treatment is performed for 5 minutes to obtain a clearcolorless solution that was then filtered with a 0.2 μm-pore size PTFEfilter head to obtain clear filtrate as a precursor solution beforereaction.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL n-hexane was added,and placed on a magnetic mixer to be fast stirred for next operation:

(4) Preparation of Quantum Dot Emulsion

The precursor solution was drawn via a microsyringe and added inton-hexane dropwise which was being fast stirred in step (3) whilemonitored under the ultraviolet lamp, until that the precursor solutionwas completely added.

(5) Demulsification

5 mL tert-butanol was added to the solution obtained in step (4) andtransferred to a centrifuge tube and centrifuged at 7500 rpm for 10minutes. After supernatant was poured out, the precipitate was theCH₃NH₃PbBr₃ quantum dot.

Embodiment 17

This embodiment adopted n-octylamine as surface ligands, dimethylsulfoxide as the first solvent and n-hexane as the second solvent formaking CHOHNH₃PbI₃ nanosheets by the following steps:

(1) Preparation of Formylammonium Bromide

The method for making formylammonium bromide was the same as that ofmethylammonium bromide;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol formylammonium bromide, 0.2mmol lead iodide, 0.4 mmol n-octylamine, 1 mL propionic acid via adropper and 10 mL dimethyl sulfoxide were added thereto, to whichultrasonic treatment is performed for 5 minutes to obtain a clearcolorless solution that was then filtered with a 0.2 μm-pore size PTFEfilter head to obtain clear filtrate as a precursor solution.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to Which 10 mL n-hexane was added,and placed on a magnetic mixer to be fast stirred for next operation:

(4) Preparation of Quantum Dot Emulsion

The precursor solution was drawn via a microsyringe and added inton-hexane dropwise which was being fast stirred in step (3), whilemonitored under the ultraviolet lamp, until that the precursor solutionwas completely added.

(5) Demulsification

10 mL methanol was added to the solution obtained in step (4) andcontinuously stirred for 30 minutes and then transferred to a centrifugetube to be centrifuged at 7500 rpm for 10 minutes. After supernatant waspoured out, the precipitate was CHOHNH₃PbI₃ nanosheets.

Embodiment 18

This embodiment adopted oleyl amine as a surface ligand, dimethylsulfoxide as the first solvent and n-heptane as the second solvent formaking CH₃CHONH₃PbCl₃ nanowires by the following steps:

(1) Preparation of Acetylammonium Chloride

The method for making acetylammonium chloride was the same as that ofmethylammonium chloride;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol acetylammonium chloride, 0.2mmol lead chloride, 0.4 mmol oleyl amine, 1 mL propionic acid via adropper and 10 mL dimethyl sulfoxide were added thereto, then to whichultrasonic treatment is performed for 5 minutes to obtain a clearcolorless solution, which was then filtered with a 0.2 μm-pore size PTFEfilter head to obtain clear filtrate as a precursor solution.

(3) Preparation of a Second Solvent

Another 10 mL isotope vial was taken, to which 10 mL n-heptane was thenadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of Quantum Dot Emulsion

The precursor solution was drawn via a microsyringe and added inton-heptane dropwise which was being fast stirred in step (3) whilemonitored under the ultraviolet lamp, until that the precursor solutionwas completely added.

(5) Demulsification

7 mL n-butanol was added to the solution obtained in step (4) andtransferred to a centrifuge tube to be centrifuged at 7500 rpm for 10minutes. After supernatant was poured out, the precipitate wasCH₃CHONH₃PbCl₃ nanowires.

Embodiment 19

This embodiment adopted phenylethylamine as a surface ligand, N-methylpyrrolidinone as the first solvent and n-heptane as the second solventfor making CH₃NH₃PbCl₃ quantum dot by the following steps:

(1) Preparation of Methylammonium Bromide

The method for making methylammonium bromide was the same as thatdescribed above;

(2) Preparation of a Precursor Solution Before Reaction

A 10 mL isotope vial was taken, 0.2 mmol methylammonium bromide, 0.2mmol lead chloride, and then 0.4 mmol phenylethylamine, 1 mL propionicacid via a dropper and 1 mL N-methyl pyrrolidinone were added thereto,then to which ultrasonic treatment is performed for 5 minutes to obtaina clear colorless solution that was then filtered with 0.2 μm-pore sizePTFE filter head to obtain clear filtrate as a precursor solution beforereaction;

(3) Preparation of a Second Solvent

Another 10 ml isotope vial was taken, to which 10 mL n-heptane was thenadded, and placed on a magnetic mixer to be fast stirred for nextoperation:

(4) Preparation of Quantum Dot Emulsion

The precursor solution was drawn via a microsyringe and added inton-heptane dropwise which was being fast stirred in step (3) whilemonitored under the ultraviolet lamp, until that the precursor solutionwas completely added.

(5) Demulsification

7 mL n-butanol was added to the solution obtained in step (4) andtransferred to a centrifuge tube to be centrifuged at 7500 rpm for 10minutes. After supernatant was poured out, the precipitate wasCH₃NH₃PbCl₃ quantum dot.

In the description of the present invention, it shall be understood thatorientation or positional relationships indicated by terms such as“center”, “upper”, “lower”, “front”, “rear”, “left”, “right”,“vertical”, “horizontal”, “top”, “bottom”, “inner” and “outer” are basedon the orientation or positional relationship as shown in the drawings,and these terms are merely for ease of the description of the presentinvention and simplifying the description, rather than indicating orimplying that the specified device or element must have a particularorientation and be constructed and operated in a particular orientation,and thus cannot be construed as limitation of the present invention.

It shall be noted that the terms “first” and “second” are merely for thepurpose of description and cannot be construed as indicting or implyinga relative importance or implying the number of the specified technicalfeatures. Thus, features defined by “first” or “second” may explicitlyor implicitly comprise one or a plurality of said features. Further, inthe description of the present invention, unless specified otherwise, “aplurality of” means two or more.

What is claimed is:
 1. A hybridized perovskite quantum dot material,comprising: a kernel, formed by R₁NH₃AB₃ or (R₂NH₃)₂AB₄, wherein R₁ is amethyl group, R₂ is an organic molecular group, A is one or moreselected from a group consisting of Ge, Sn, Pb, Sb, Bi, Cu and Mn, B isone or more selected from a group consisting of Cl, Br and I, A and Bform a coordination octahedral structure, and R₁NH₃ or R₂NH₃ is filledin gaps of the coordination octahedral structure; and a surface ligandformed on a surface of the kernel and the surface ligand being anorganic acid or organic amine.
 2. The hybridized perovskite quantum dotmaterial according to claim 1, wherein the surface ligand is divergent,wrapping out of the surface of the kernel.
 3. The hybridized perovskitequantum dot material according to claim 1, wherein R₂ is a long-chainorganic molecular group.
 4. The hybridized perovskite quantum dotmaterial according to claim 1, wherein the surface ligand is an organicacid or a long-chain organic amine.
 5. The hybridized perovskite quantumdot material according to claim 4, wherein the organic acid comprises asaturated or an unsaturated alkyl acid with at least three carbon atoms.6. The hybridized perovskite quantum dot material according to claim 4,wherein a molecular formula of the long-chain organic amine is RNH₂, andR is a saturated linear or branched alkyl group, or an unsaturatedlinear or a branched alkyl group.
 7. The hybridized perovskite quantumdot material according to claim 4, wherein the long-chain organic amineis an alkyl or aryl amine with from 4 to 24 carbon atoms.
 8. Ahybridized perovskite quantum dot material, comprising: a kernel, formedby R₁NH₃AB₃ or (R₂NH₃)₂AB₄, wherein A and B form a coordinationoctahedral structure, R₁NH₃ or R₂NH₃ is filled in gaps of thecoordination octahedral structure, R₁ is methyl, R₂ is a long-chainorganic molecular group, A is one or more selected from a groupconsisting of Ge, Sn, Ph, Sb, Bi, Cu and Mn, and B is one or moreselected from a group consisting of Cl, Br and I; and a surface ligandthat is divergent, wrapping out of the surface of the kernel, andwherein the surface ligand is an organic acid or a long-chain organicamine.
 9. The hybridized perovskite quantum dot material according toclaim 8, wherein the organic acid is a saturated alkyl acid that itsformula is C_(n)H_(2n+1)COOH (n≥2), or an unsaturated alkyl acid thatits formula is C_(n)H_(2n−1)COOH (n≥2).
 10. The hybridized perovskitequantum dot material according to claim 8, wherein a molecular formulaof the long-chain organic amine is RNH₂, and R is a saturated linear ora branched alkyl group, or an unsaturated linear or a branched alkylgroup.
 11. The hybridized perovskite quantum dot material according toclaim 8, wherein the long-chain organic amine is an alkyl or aryl aminewith from 4 to 24 carbon atoms.